This invention relates to 1-substituted-phenyl-3-substituted-2-thioxo-4,5-imidazolidinediones and 2,4,5-imidazolidinetriones which have activity as herbicides, to compositions which contain these compounds and to methods of use of these compounds. In particular, the present invention pertains to 2-thioxo-4,5-imidazolidinediones or 2,4,5-imidazolidinetriones wherein a substituted phenyl ring is linked to the heterocyclic ring.
Certain 1-substituted phenyl-2-thioxo-4,5-imidazolidinediones and 2,4,5-imidazolidinetriones are known aldose reductase inhibitors (see U.S. Pat. No. 4,985,453), agricultural herbicides (see U.S. Pat. Nos. 2,895,817, 3,418,334, and 4,283,547), agricultural fungicides (see Japanese Patent disclosure 53018569), and agricultural insecticides (see International Patent Application No. WO 93/22289 A1). However, there is still a need for herbicidal compounds which have superior efficacy over those already known in the art.
We have discovered that certain compounds of this invention are surprisingly effective as pre-emergent and post-emergent herbicides. These compounds are represented by formula I 
wherein
R is hydrogen, (C1-C8)alkyl, (C3-C6)cycloalkyl, (C2-C6)alkenyl, (C3-C6)alkynyl, (C1-C4)alkoxy(C1-C4)alkyl, (C3-C6)cycloalkoxy(C1-C4)alkyl, (C2-C6)alkenyloxy(C1-C4)alkyl, (C3-C6)alkynyloxy(C1-C4)alkyl, (C1-C12)alkylcarbonyl, (C1-C4)alkoxycarbonyl, (C2-C6)alkenyloxycarbonyl, cyano, dialkylamino, or (C1-C6)alkylsulfonyl;
X1 is hydrogen or halo;
X2 is halo, cyano, or nitro;
X4 is hydrogen or halo;
X3 is (C1-C8)haloalkyl, (C1-C8)alkoxy, (C3-C6)cycloalkoxy, (C2-C6)alkenyloxy, (C3-C6)alkynyloxy, (C1-C12)alkylcarbonyl, (C1-C4)alkoxycarbonyl, (C2-C6)alkenyloxycarbonyl, (C3-C6)alkynyloxycarbonyl, (C1-C8)alkylsulfonylamino, (C1-C8)alkylsulfonylalkylamino, (C1-C4)alkoxycarbonylmethoxy, (C1-C4)alkoxycarbonylethoxy; or Q;
xe2x80x83wherein Q is 
wherein R1 is NH2, OH, or (C1-C4)alkyl; and each W is independently oxygen or sulfur;
or, when X1 is halo and X4 is hydrogen, then X2 and X3 may form a 5- or 6-membered heterocyclic ring fused to the phenyl ring to form a bicyclic moiety of the formula: 
wherein
L is oxygen or sulfur;
R2 is hydrogen or (C1-C4)alkyl;
R3 is hydrogen; (C1-C6)alkyl, (C1-C6)haloalkyl, (C2-C6)alkenyl, (C3-C6)alkynyl; (C1-C4)alkoxyalkyl; (C2-C6)alkenyloxyalkyl; (C3-C6)alkynyloxyalkyl; cyanoalkyl; amino, or hydroxy; R4 is hydrogen, (C1-C3)alkyl, or fluorine;
or when X1 and X2 are halo, then X3 and X4 form a 5- or 6-membered heterocyclic ring fused to the phenyl ring to which they are attached to form a bicyclic moiety having the structure 
wherein
Y is oxygen, sulfur or xe2x80x94NR6 wherein R6 is hydrogen, (C1-C6)alkyl, (C3-C5)alkenyl or (C3-C6)alkynyl;
Yxe2x80x2 is oxygen, sulfur, xe2x80x94NR6, or xe2x80x94CO;
R5 is hydrogen, halo, (C1-C6)alkyl, (C3-C6)cycloalkyl, (C2-C6)alkenyl, or (C3-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, cyano, (C1-C6) hydroxyalkyl, xe2x80x94CO2R8, a formyl group, an acyl group, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylthio, (C1-C6)haloalkylsulfinyl, (C1-C6)haloalkylsulfonyl, or a carboxyl group;
R6 is hydrogen, (C1-C6)alkyl, (C3-C6)alkenyl, or (C3-C6)alkynyl;
R7 is hydrogen, halo, (C1-C6)alkyl, (C1-C6)haloalkyl, an acyl group, or a nitro;
and agronomically acceptable salts thereof.
The term xe2x80x9calkylxe2x80x9d includes both branched and straight chain alkyl groups such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, isooctyl, nonyl, decyl, undecyl, dodecyl and the like. The term xe2x80x9ccycloalkylxe2x80x9d refers to a cyclic aliphatic ring structure such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like. The term xe2x80x9chaloalkylxe2x80x9d refers to an alkyl group substituted with one or more halo groups. The term xe2x80x9chaloxe2x80x9d refers to fluoro, chloro, bromo or iodo.
The term xe2x80x9calkylsulfonylalkylxe2x80x9d refers to an alkyl group substituted with an alkylsulfonyl (alkyl-SO2) group, for example methylsulfonylmethyl. The term xe2x80x9calkylsulfinylalkylxe2x80x9d refers to an alkyl group substituted with an alkylsulfinyl (alkyl-SO) group, for example methylsulfinylmethyl.
The term xe2x80x9calkenylxe2x80x9d refers to an ethylenically unsaturated hydrocarbon group, straight or branched, having 1 or 2 ethylenic bonds. The term xe2x80x9chaloalkenylxe2x80x9d refers to an alkenyl group substituted with one or more halo groups. The term xe2x80x9calkynylxe2x80x9d refers to an unsaturated hydrocarbon group, straight or branched, having 1 or 2 acetylenic bonds. The term xe2x80x9calkoxyxe2x80x9d includes both branched and straight chain alkyl groups attached to a terminal oxygen atom such as, for example, methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy and the like. The term xe2x80x9chaloalkoxyxe2x80x9d refers to an alkoxy group substituted with one or more halo groups.
The term xe2x80x9calkylthioxe2x80x9d includes both branched and straight chain alkyl groups attached to a terminal sulfur atom. The term xe2x80x9chaloalkylthioxe2x80x9d refers to an alkylthio group substituted with one or more halo groups.
Agronomically acceptable salts may be formed by complexation of the compounds of the current invention with metal salts such as zinc chloride or iron chloride.
For purposes of this invention, unless otherwise indicated, all percentages, parts, and ratios are by weight and all ranges are inclusive and combinable.
Preferred compounds are compounds of formula I, wherein W is oxygen or sulfur; R is, (C1-C6)alkyl, (C1-C4)haloalkyl, (C4-C6)cycloalkyl, (C2-C5)alkenyl, (C3-C6)alkynyl, (C1-C3)alkoxyalkyl, (C4-C6)cycloalkoxyalkyl, (C2-C5)alkenyloxyalkyl, (C3-C6)alkynyloxyalkyl; X1 is fluoro; X2 is halo; X4 is hydrogen or halo; X3 is (C1-C4)alkoxy, (C3-C6)cycloalkoxy, (C2-C6)alkenyloxy, (C3-C6)alkynyloxy, (C1-C4)alkoxycarbonyl, (C2-C6)alkenyloxycarbonyl, (C3-C6)alkynyloxycarbonyl, (C1-C6)alkylsulfonylamino, (C1-C4)alkylsulfonylalkylamino, (C1-C4)alkoxycarbonylmethoxy, or (C1-C3)alkoxycarbonylethoxy; or when X1 is fluoro and X4 is hydrogen, then X2 and X3 form a 5- or 6 membered heterocyclic ring fused to the phenyl ring structure to form the bicyclic moiety wherein L is oxygen; R2 is hydrogen or alkyl; R3 is alkyl, haloalkyl, alkenyl, alkynyl; alkoxyalkyl; alkenyloxyalkyl; alkynyloxyalkyl; cyanoalkyl; amino, or hydroxy; and R4 is hydrogen, (C1-C3)alkyl, or fluorine; and agronomically acceptable salts thereof.
More preferred compounds are compounds of Formula II 
wherein: W is oxygen or sulfur; R is (C1-C3)alkyl, (C1-C3)haloalkyl, (C5-C6)cycloalkyl, (C2-C5)alkenyl, (C3-C6)alkynyl; R3 is (C1-C3)alkyl, (C1-C3)haloalkyl, (C2-C5)alkenyl, (C3-C6)alkynyl, (C1-C3)alkoxyalky, (C2-C5)alkenyloxyalkyl, (C3-C6)alkynyloxyalkyl; cyanoalkyl; and agronomically acceptable salts thereof.
The compounds of Formula I of the present invention can be prepared by the following processes: 
Substituted phenylureas (W=O) or thioureas (W=S) are reacted with oxalyl chloride in a solvent inert under the reaction conditions, e.g., chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran or dioxane to give compounds of Formula I, optionally in the presence of the bases such as Et3N, pyridine, NaOH, KOH, Na2CO3, K2CO3, NaHCO3 at a temperature from xe2x80x9440xc2x0 C. to the boiling point of the solvent for 3 minutes to 48 hours. 
Substituted phenylanilines are reacted with isocyanates (W=O) or isothiocyanates (W=S), which are commercially available or can be prepared by known methods, in a solvent inert under the reaction conditions, e.g. chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran, alcohols, or dioxane to give phenylureas or phenylthioureas, optionally in the presence of the bases such as Et3N or pyridine as catalyst at a temperature from xe2x80x9440xc2x0 C. to the boiling point of the solvent for 3 minutes to 48 hours. 
Substituted phenylisocyanates (W=O) or isothiocyanates (W=S), which are commercially available or can be prepared by known methods, are reacted with amines or anilines in a solvent inert under the reaction conditions, e.g., chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran or dioxane to produce phenylureas or phenylthioureas, optionally in the presence of the bases such as Et3N or pyridine as catalyst at a temperature from xe2x80x9440xc2x0 C. to the boiling point of the solvent for 3 minutes to 48 hours. All amines or anilines are commercially available or can be prepared by known methods. 
Substituted anilines are reacted with phosgene, diphosgene, triphosgene or oxalyl chloride in a solvent inert under the reaction conditions, e.g., chloroform ,dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran or dioxane to prepare phenyisocyanates or phenylisothiocyanates optionally in the presence of the bases such as Et3N or pyridine as catalyst at a temperature from xe2x80x9440xc2x0 C. to the boiling point of the solvent for 3 minutes to 48 hours (c.f.Chemistry and Technology of Isocyanates: author: Henry Ulrich, Publisher: John Willy and Sons, page 1-192).
Anilines may be obtained from the nitro substituted benzene (made by known methods such as those described in European Patent Application No. 0 083 055 A2) by reacting with hydrogen or reductive metals such as iron, zinc, and titanium etc. in compatible solvents, such as chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, DMF, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, ethanol or combined with an inorganic acid such as hydrochloric acid, at a temperature from xe2x80x9440xc2x0 C. to the boiling point of the solvent for 3 minutes to 48 hours. 
Alternatively, compounds of Formula I may be prepared by reacting compounds of Formula I-1 with an alkyl halide or alkyl sulfonylester in a solvent inert under the reaction conditions, e.g., chloroform ,dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetone, DMF, tetrahydrofuran or dioxane, optionally in the presence of bases such as Et3N, pyridine NaOH, KOH, Na2CO3, K2CO3, NaHCO3 or sodium hydride at a temperature from xe2x80x9440xc2x0 C. to the boiling point of the solvent for 3 minutes to 48 hours. 
Compounds of Formula I-1 may be prepared by reacting compounds of Formula III with a base such as Et3N, pyridine NaOH, KOH, Na2CO3 or K2CO3, in a solvent inert under appropriate reaction conditions, e.g., chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetone, DMF, tetrahydrofuran or dioxane, at a temperature from xe2x80x9440xc2x0 C. to the boiling point of the solvent for 3 minutes to 48 hours. 
Compounds of Formula VI, in turn, can be prepared by reacting compounds of Formula IV, which can be prepared as shown in equation 4, or are commercially available, with ethyl oxamate, which is commercially available, in a solvent inert under the reaction conditions, e.g., chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran or dioxane, optionally in the presence of the bases such as Et3N or pyridine as catalyst at a temperature from xe2x80x9440xc2x0 C. to the boiling point of the solvent for 3 minutes to 48 hours. 
Certain compounds of the Formula I may be obtained by reacting compounds of Formula I-2, which can be prepared according to equation 1) with alkyl halide or alkyl sulfonylesters in a solvent inert under the reaction conditions, e.g., chloroform ,dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate,acetone, DMF, tetrahydrofuran or dioxane, optionally in the presence of the bases such as Et3N, pyridine NaOH, KOH, Na2CO3, K2CO3, NaHCO3 or sodium hydride at a temperature from xe2x80x9440xc2x0 C. to the boiling point of the solvent for 3 minutes to 48 hours. Alkyl halide or alkyl sulfonylesters are commercially available or can be prepared by known methods.